Spectroscopic and Electrochemical Probes of Electronic Coupling in Some Cyanide-Bridged Transition Metal Donor/Acceptor Complexes

摘要: The effects of donor−acceptor (D/A) electronic coupling, HDA, on the spectroscopic and electrochemical properties several series CN--bridged transition metal complexes have been examined. employed were formed by ruthenation M(L)(CN)2n+ parent (for n = 0, M Ru(II) or Fe(II), L bpy phen; for 1, Cr(III), Rh(III), Co(III), bpy, phen, a tetraazamacrocyclic ligand). observed half-wave potentials resulting D/A spanned 300−350 mV range in contrast to about 80 expected basis oscillator strength, hDA, charge-transfer MM‘CT absorption band geometrical distance between donor acceptor, rDA. Different exhibit different correlations E1/2 hDA. Several factors found contribute these differences:  (a) symmetry effects; (b) solvational differences that arise when nonbridging ligands are changed; (c) arisin...